US5110842A - Electron-beam cured sheet-type foam - Google Patents

Electron-beam cured sheet-type foam Download PDF

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US5110842A
US5110842A US07/598,646 US59864690A US5110842A US 5110842 A US5110842 A US 5110842A US 59864690 A US59864690 A US 59864690A US 5110842 A US5110842 A US 5110842A
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copolymer
foam
ethylene
weight
parts
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Nario Uejikkoku
Masashi Takeda
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/915—Utilizing electrical or wave energy during cell forming process

Definitions

  • the present invention relates to a foam, and more particularly to a sheet-type foam which is cured by an electron beam.
  • Electron-beam cured foams have been used as cushioning materials in automobile interiors, and a heat-resisting and heat-insulating materials.
  • Japanese Patent Laying-Open No. 265935/1988 discloses a cured foam consisting of an olefin resin comprising linear very-low-density polyethylene of more than 10 wt. %.
  • the linear very-low-density polyethylene is made by copolymerizing ethylene with an ⁇ -olefin having more than 4 carbons.
  • the olefin resin may be a polymer made from olefin monomers, such as polypropylene, or a copolymer mixture of ethylene/ethylacrylate.
  • the linear very-low-density polyethylene may be composed by a process in which ethylene is copolymerized with an ⁇ -olefin having more than 4 carbons, such as butene-1, hexene-1, octene-1, 4-methylpentene-1, in order to add an appropriate number of short branches to the main linear chains, whereby the density is decreased.
  • an ⁇ -olefin having more than 4 carbons such as butene-1, hexene-1, octene-1, 4-methylpentene-1
  • the mixture was formed into a sheet of 1.5 mm thickness by an extruder.
  • both surfaces were irradiated by an electron beam of 2.0 Mrad in an electron-beam irradiation apparatus.
  • the sheet was then uniformly transported through a hot air stove at 250° C. for heat foaming, whereby a sheet-type foam of about 4 mm in thickness was obtained.
  • the obtained cross-linked foam is of inferior tensile strength and dimensional stability, although it has good flexibility. That is, a foam produced in direct accordance with the technology disclosed in Japanese Patent Laying-Open No. 265935/1988 results in insufficient tensile strength and insufficient dimensional stability, due to inappropriateness in the selection of resins and the mixing ratio.
  • Japanese Patent Laying-Open No. 155232/1981 and Japanese Patent Laying-Open No. 157839/1983 disclose a resin made of a copolymer of ethylene of which melting point ranges from 117° C. to 123° C. and density ranges from 0.890 g/cm 3 to 0.910 g/cm 3 , and an ⁇ -olefin having 4 to 8 carbons.
  • this resin is not comprised of 3 components, as in the above example from the prior art.
  • an electron-beam cured sheet-type foam comprises a polypropylene type resin (A) of 100 parts by weight of which main component is propylene; a copolymer resin (B) of 5 to 40 parts by weight, composed of ethylene and at least one selected from the group consisting of acrylic acid, ethylacrylate, maleic acid anhydride and vinylacetate; and a copolymer resin (C) of 10 to 80 parts by weight ethylene, of which melting point ranges from 117° C. to 123° C. and density ranges from 0.890 g/cm 3 to 0.910 g/cm 3 , and an ⁇ -olefin having 4 to 8 carbons.
  • This foam ranges from 20 to 60% in gel percent and from 5 to 40 in expansion ratio.
  • This foam may preferably be 50 kg/cm 2 .% or more in tensile strength at 150° C., and 5% or less in size-change ratio at 120° C., or size stability.
  • a foam of improved flexibility, tensile strength, dimensional stability, and processability in molding may be obtained by mixing the resins (A), (B) and (C) in a proper ratio, and by electron-beam curing prior to foaming.
  • a polypropylene type resin (A) comprising propylene for use in a foam according to the present invention is, for example, a propylene homo-polymer; or a random copolymer, block copolymer or random/block copolymer of propylene, and at least one selected from the group consisting of ethylene and butane.
  • the amount of ethylene and/or butene-1 in the copolymer may range from 2 to 35 weight percent, preferably from 3 to 30 weight percent. More preferably, the copolymer may be a random copolymer including ethylene of 4 to 15 weight percent.
  • the copolymer resin (B) may include ethylene and at least one compound of 5 to 30 weight percent (preferably, 8 to 25 weight percent) selected from the group consisting of acrylic acid, ethylacrylate, maleic acid anhydride and vinylacetate. More preferably, the copolymer (B) may be ethylene-ethylacrylate (EEA) comprising ethylacrylate of 8 to 18 percent, or a three-component copolymer of ethylene/ethylacrylate/maleic-acid-anhydride (EEA-MAH), including ethylacrylate and maleic acid anhydride of 8 to 18 weight percent in total.
  • ESA ethylene-ethylacrylate
  • ESA-MAH three-component copolymer of ethylene/ethylacrylate/maleic-acid-anhydride
  • the copolymer resin (C) of ethylene and ⁇ -olefin having 4 to 8 carbons ranges from 117° to 123° C. in melting point, and from 0.890 to 0.910 g/cm 3 in density.
  • the copolymer (C) may include an ⁇ -olefin having 4 to 6 carbons, and may range from 117° to 123° C. in melting point and from 0.895 to 0.905 g/cm 3 in density.
  • the copolymer (C) of ethylene and ⁇ -olefin may be an ethylene/ ⁇ -olefin copolymer as disclosed in Japanese Patent Laying-Open No. 157839/1983.
  • the copolymer (C) in the foam according to the present invention is different from the linear very-low-density polyethylene as described in Japanese Patent Laying-Open No. 265935/1988, viz., Ultzex (Mitsui Petrochemical Industries Ltd.) and Excelen (Sumitomo Chemical Co., Ltd.).
  • the polyethylene used in Japanese Patent Laying-Open No. 265935/1988 has a melting point 4° to 7° C. lower than that used in the present invention.
  • the lower melting point deteriorates the dimensional stability of the foam.
  • the polyethylene used in the present invention has a higher melting point at low density, providing good flexibility and low size-change rate at 120° C.
  • the mixing ratio of resin components (A), (B) and (C) is defined as follows: the component (A) is 100 parts by weight, the component (B) is 5 to 40 parts by weight (preferably, 5 to 25 parts by weight), and the component (C) is 10 to 80 parts by weight (preferably, 20 to 50 parts by weight). If the proportion of the component (B) is more than 40 parts by weight, the size stability (size-change rate at 120° C.) of the obtained foam becomes more than 5 percent. If the proportion of component (B) is lower than 5 parts by weight, the obtained foam cannot satisfy the required levels of flexibility, heat resistance, tensile strength and molding processability. Particularly, the obtained foam lacks sufficient tensile strength at high temperatures.
  • the obtained foam has the same characteristics as those of a foam made from a mixture of the components (A) and (C). If a foam contains an excess of the component (A), the obtained foam lacks sufficiently high flexibility, although it has high shock resistance and dimensional stability. If a foam contains an excess of the component (C), the obtained foam has inferior heat resistance, although it has high flexibility. If the proportion of the component (C) is less than 10 parts by weight, the flexibility of the obtained foam deteriorates. Moreover, if the proportion of the component (C) is more than 80 parts by weight, the size stability deteriorates, although good flexibility may be obtained.
  • the foam ranges from 20 to 60 percent in gel percent and from 5 to 40 in expansion rate.
  • the gel percent is lower than 20 percent, the dimensional stability of the obtained foam deteriorates due to gel shortage. Furthermore, the predetermined density cannot be obtained and the formed surfaces of the foam are rough, due to the fact that a gas is generated inside the foam during production which disrupts the surfaces. Moreover, sufficient tensile strength at high temperatures cannot be obtained. If the gel percent is more than 60 percent, the obtained foam tends too strongly to retain its shape resulting in greater than 5 percent of dimensional stability (size-change rate at 120° C.). The flexibility also deteriorates.
  • the expansion ratio must range from 5 to 40. If the expansion ratio is lower than 5, the flexibility deteriorates inasmuch as the foam becomes too hard, although the tensile strength and the molding processability remain sufficient. If the expansion rate is more than 40, the shock-absorbing ability deteriorates inasmuch as the obtained foam becomes too soft, although the flexibility remains sufficient.
  • the foam may be 50 kg/cm 2 .% or more in tensile strength at 150° C. If the tensile strength is lower than 50 kg/cm 2 .%, the obtained foam becomes ruptured, because the tensile strength of the foam is not sufficient at high temperatures to correspond with the expansion and the expansion stress of the facing material (such as a sheet of vinylchloride), when the foam is heat-processed after being laminated with the facing material.
  • the facing material such as a sheet of vinylchloride
  • Cured foams made of conventional resin proportions have a problem in that only a few kinds of facing material may be used in a heat molding process due to the low expansion stress of the foams.
  • foam according to the present invention has 50 kg/cm 2 .% or more in tensile strength, so that it is superior to conventional foams.
  • Foam according to the present invention is of improved tensile strength at high temperatures, whereby less disuniformity in thickness of product occurs, and heat-molding processability is improved.
  • the molding processability (L/D) can be expanded to 1.2.
  • the dimensional stability (size-change rate at 120° C.) of a foam according to the present invention is preferably 5 percent or less. If the dimensional stability is more than 5 percent, foam shrinkage is so great that products in which the inclusion of a heat-process method is essential cannot be obtained.
  • the 25%-compressive hardness of the foam according to the present invention preferably ranges from 0.1 to 1.0 kg/cm 2 at ordinary temperatures. If the compressive hardness is more than 1.0 kg/cm 2 , the tensile strength of foam becomes so great that its tactility deteriorates. If the compressive hardness is lower than 0.1 kg/cm 2 , the foam becomes so soft that a "reaching-bottom feeling" results (i.e., a feeling of reaching the opposite surface when the foam is pressed by a finger). Furthermore, foam of weak tensile strength deteriorates handling characteristics in manufacturing and transforming processes.
  • the 5%-tensile stress of the foam according to the present invention may range from 10 to 100 kg/cm 2 at ordinary temperature. If the stress is more than 100 kg/cm 2 , the shock absorbing ability deteriorates and the tensile strength becomes too great. If the stress is lower than 10 kg/cm 2 , the tensile strength becomes too weak, although the flexibility is adequate.
  • the 25%-compressive hardness and the 5%-tensile stress at ordinary temperature may be used as a measure of suppleness flexibility. Foams of which characteristics are within the above ranges will have suppleness noticeably different from those of conventional foams, when such foams are evaluated after they are laminated with various kinds of facing material and processed to form products.
  • the foam according to the present invention is a sheet.
  • the foam may be more than 10 m long, and may be rolled in forming a material product.
  • the long sheet may be processed in several continuous manufacturing steps in order to decrease losses during the steps.
  • the resin components (A), (B) and (C), powdered into 32-mesh-passing size, are provided, of which proportions are within the ranges of the present invention.
  • the components are fed into a high-speed mixing apparatus (such as a Henschel mixer or a super mixer).
  • a high-speed mixing apparatus such as a Henschel mixer or a super mixer.
  • an ordinary chemical foaming agent of the decomposable type for example, azodicarbonamide, dinitrosopentamethylene-tetramine, etc.
  • other additives may also be included. Thereby, initial mixing is carried out.
  • the obtained material is fed into an extruder heated at 130° to 190° C., and melt-diffusion mixing is effected, producing a long sheet which is 0.5 to 6 mm in thickness.
  • melt-diffusion mixing is effected, producing a long sheet which is 0.5 to 6 mm in thickness.
  • the obtained sheet must be cured in order not to allow interior gas generated by the decomposition of the foaming agent to escape during the foaming process.
  • a conventional ionizing radiation method may be used.
  • a conventional peroxide compound can be added prior to irradiation; furthermore, if desired, a multi-functional monomer of divinylbenzene, trimethylolpropane triacrylate, pentaerythritol triacrylate, etc.; a multi functional dimer of those; or a multi functional trimer of those may be added as a crosslinking promoting agent.
  • Added within the scope of the present invention may be an inorganic filler such as calcium carbonate, talc, glass balloon, glass fiber, etc.; an antistatic agent; a flame retarder; and a colorant.
  • the obtained cured sheet is introduced into a heated-air atmosphere or onto a chemical liquid such as silicon oil, of which temperature is 10° to 100° C. higher than the decomposing temperature of the foaming agent, whereby the foaming agent is rapidly decomposed to make the sheet-type cured foam.
  • a chemical liquid such as silicon oil, of which temperature is 10° to 100° C. higher than the decomposing temperature of the foaming agent, whereby the foaming agent is rapidly decomposed to make the sheet-type cured foam.
  • a foam having an adhesive layer, or a cohesive layer formed of a coating material can be laminated with a sheet of facing material, a film, another kind of foam, a metallic foil, a sheet of paper, a piece of nonwoven fabric made of natural fiber or synthetic fiber, or a piece of synthetic leather.
  • the obtained laminated product can be molded by various methods.
  • the melting point is a temperature at the highest peak of endothermic peaks in measurement with a differential spectrum calorimeter (DSC).
  • the density is measured in accordance with JISK6767.
  • the foam to be measured is broken into small pieces, and 0.2 g pieces of the foam are selected by accurate weighing.
  • the weighed pieces are soaked in tetralin at 135° C. for 2 hours, to elute soluble substances.
  • the insoluble part is taken out from the tetralin, and the tetralin remaining in the insoluble part is removed by acetone.
  • the acetone is removed by hot water at 40° C.
  • the insoluble part is then dried in a vacuum drier at 100° C. for 1 hour, and the weight w1(g) of the insoluble part is measured.
  • the gel percent (%) is calculated by the following formula, wherein 10 pieces of the foam should be used.
  • a 10 ⁇ 10-cm piece is taken from a sheet-type foam.
  • the piece is measured with respect to its thickness t (cm) and its weight w2 (g).
  • the expansion rate is calculated by the following formula, wherein 10 sample pieces are used.
  • a 1 ⁇ 10-cm piece is taken from a sheet-type foam, and measured with respect to its thickness t(cm).
  • the piece of foam is set between chucks in a tensilon-type tensile tester within a heat box at 150° C. The distance between the chucks is 5 cm.
  • the piece of foam is protected by paper or the like at the chucked portions, so that it will not be fractured at those portions. 5 minutes after the piece is set in the heat box, the piece is stretched at a tensile speed of 200 mm/min.
  • the rupture stress s1(kg) and the rupture extension s2(cm) are recorded on a sheet of record paper.
  • the tensile strength at 150° C. (kg/cm 2 .%) can be calculated by the following formula, wherein 5 pieces of foam are used. ##EQU1## where s1 is 0.3 kg/cm 2 or more, s2 is 100% or more.
  • a 10 ⁇ 10-cm piece is taken from a sheet-type foam, and measured in thickness t(mm) at the center.
  • the piece is heated for 1 hour in a hot air drier at 120° C. Subsequently, the piece is left for 2 hours at room temperature, and then its size is measured.
  • the 120° C.-Size-Change rate (%) can be calculated by the following formula. ##EQU2## where TD signifies the lengthwise direction, MD signifies the widthwise direction.
  • the Compressive Hardness is measured in accordance with JIS K-6767.
  • a 1 ⁇ 10-cm piece is taken from a sheet-type foam, and its thickness t(cm) is measured.
  • the piece is set between chucks separated by a distance of 5 cm in a tensilon-type tensile tester, and stretched at 20 mm/min.
  • the changes of stress and elongation are recorded on a sheet of paper, and then the stress s1 (kg) of the piece is measured when it has been stretched five percent.
  • the 5%-expansion stress at ordinary temperature is calculated by the following formula.
  • Cylindrical metal molds of which the depth (L)/diameter(D) ratio varies at intervals of 0.05 are used.
  • a foam or laminated sheet is vacuum-molded at 160° to 180° C. by a vacuum molding machine.
  • the maximum ratio at which the foam forms a molding without any breaks is determined as the value of molding processability.
  • Tables 1A and 1B show the resin composition, the mixing ratio, the curing methods and the characteristics of the foams according to the present invention.
  • random means random copolymer
  • block means block copolymer
  • homo means homo polymer.
  • EPC means propylene/ethylene copolymer
  • BPC means propylene/butane copolymer
  • EEA means ethylene/ethylacrylate
  • EVA means ethylene/vinylacetate copolymer
  • EA.MAH means (ethylene/ethylacrylate/maleicacid-anhydride) terpolymer.
  • Et-Bt of ethylene/ ⁇ -olefin copolymer means a copolymer formed by the polymerization of ethylene with butane as an ⁇ -olefin.
  • the low-density polyethylene is made by the high pressure method, and the high-density polyethylene is made by the low pressure method.
  • the linear very-low-density polyethylene is a polyethylene of which density is 0.910 g/cm 3 or lower, and which is made by the high-pressure ion polymerization method and the intermediate-low-pressure solution polymerization method.
  • One-hundred-fifty-kg mixtures of the resin components, a foaming agent, and other additives were each fed into a 500-litter Henschel mill. Each portion of the obtained mixed material was fed into an extruder of which cylinder temperature was 170° to 180° C. to carry out melt-mixing, whereby a long sheet of 1.5 mm thickness and 500 mm width was formed. The long sheet was set in an electron-beam irradiating device, and then it was cured with 2 to 10 Mrad electron-beam radiation. The obtained foamable cured sheet was introduced uniformly onto silicon oil of which temperature ranges from 210° to 240° C., thereby foaming the sheet.
  • the foamed sheet was dried by hot air, whereby a sheet-type cured foam was obtained.
  • the obtained foams ranged from 2.5 to 3.5 mm in thickness and from 950 to 1100 mm in width.
  • the foams according to the present invention as shown in Table 1B, had high degrees of flexibility, tensile strength, dimensional stability and molding processability, since the resin components, the mixing ratio, the curing method and the cross-linking density were chosen appropriately. Particularly, 25%-compressive hardness and 5%-expansion stress as parameters of flexibility were superior, so that the obtained flexible foams had a good tactility. Furthermore, the obtained foams had a tensile strength at high temperature which had not been achieved by conventional foams.
  • Tables 2A and 2B show the resin component, the mixing ratio, the curing method and the characteristics of the obtained foams with regard to comparative examples.
  • the comparative examples were cured by the electron-beam curing method in the same manner as in the examples according to the present invention, or in the curing method with peroxide compounds, and foamed in the same way as in the examples according to the present invention.
  • Comparative examples 1 to 3 were made of ethylene/ ⁇ -olefin copolymer. As shown in Table 2B, the comparative examples were inferior, at least in terms of flexibility, tensile strength and dimensional stability, since the resin components, the mixing ratio and the curing method were apart from the scope of the present invention. In particular, the comparative examples were much inferior in terms of tensile strength at high temperature and 120° C. size-change rate. Comparative examples 4 to 7 were made of linear very-low-density polyethylene (EXCELEN). As shown in Table 2B, the comparative examples were inferior, at least in terms of flexibility, tensile strength and dimensional stability, since the resin components, the mixing ratio and the curing method were apart from the scope of the present invention.
  • EXCELEN linear very-low-density polyethylene
  • the parts marked by an asterisk are apart from the scope of the present invention.
  • the foams according to the present invention are superior in terms of flexibility, or tactility in particular.
  • a high degree of molding processability can be obtained in accordance with the present invention, because the foams have a high degree of tensile strength, particularly at high temperatures.
  • the foams according to the present invention also have sufficient dimensional stability, whereby they may be suitable as a damping material, for application to the doors, the ceiling, the instrument panel, etc. of automobiles interiors.
  • the foams according to the present invention can be also applied to the base material of heat-resist adhesive tape, the base material of packagings, and heat-resisting and heat-insulate molding products, including various kinds of valves and pipes, etc., by virtue of the above characteristics.

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Abstract

An electron-beam cured sheet-type foam comprises: a polypropylene type resin (A) of 100 parts by weight of which main component is polypropylene; a copolymer resin (B) of 5 to 40 parts by weight which is made of ethylene and at least one selected from the group consisting of acrylic acid, ethylacrylate maleic acid anhydride and vinylacetate; and a copolymer resin (C) made of ethylene and an α-olefin of 4 to 8 carbon atoms, having a melting point of 117° C. to 123° C. and a density of 0.890 g/cm3 to 0.910 g/cm3. This foam contains 20 to 60 percent in gel content and has an expansion ratio of 5 to 40.

Description

TECHNICAL FIELD
The present invention relates to a foam, and more particularly to a sheet-type foam which is cured by an electron beam.
BACKGROUND ART
Electron-beam cured foams have been used as cushioning materials in automobile interiors, and a heat-resisting and heat-insulating materials.
Japanese Patent Laying-Open No. 265935/1988 discloses a cured foam consisting of an olefin resin comprising linear very-low-density polyethylene of more than 10 wt. %. The linear very-low-density polyethylene is made by copolymerizing ethylene with an α-olefin having more than 4 carbons. According to the disclosure, the olefin resin may be a polymer made from olefin monomers, such as polypropylene, or a copolymer mixture of ethylene/ethylacrylate. The linear very-low-density polyethylene may be composed by a process in which ethylene is copolymerized with an α-olefin having more than 4 carbons, such as butene-1, hexene-1, octene-1, 4-methylpentene-1, in order to add an appropriate number of short branches to the main linear chains, whereby the density is decreased.
The above document further discloses the following example. Ethylene/propylene random copolymer of 35 parts by weight having density of 0.89 g/cm3, Melt Index of 7.0 g/10 min, and melting point of 145° C.; high-density polyethylene of 30 parts by weight having density of 0.957 g/cm3 and MI of 6.5 g/10 min; linear very-low-density ethylene/4-methylpentene-1 copolymer of 35 parts by weight having density of 0.905 g/cm3 and MI of 0.0 g/10 min; azodicarbonamide, as a foaming agent, of 15 parts by weight; trimethylpropane-trimethacrylate of 3.0 parts by weight; and a heat stabilizer of 0.5 parts by weight were mixed. The mixture was formed into a sheet of 1.5 mm thickness by an extruder. In order to cross-link the sheet, both surfaces were irradiated by an electron beam of 2.0 Mrad in an electron-beam irradiation apparatus. The sheet was then uniformly transported through a hot air stove at 250° C. for heat foaming, whereby a sheet-type foam of about 4 mm in thickness was obtained.
The obtained cross-linked foam is of inferior tensile strength and dimensional stability, although it has good flexibility. That is, a foam produced in direct accordance with the technology disclosed in Japanese Patent Laying-Open No. 265935/1988 results in insufficient tensile strength and insufficient dimensional stability, due to inappropriateness in the selection of resins and the mixing ratio.
Additionally, Japanese Patent Laying-Open No. 155232/1981 and Japanese Patent Laying-Open No. 157839/1983 disclose a resin made of a copolymer of ethylene of which melting point ranges from 117° C. to 123° C. and density ranges from 0.890 g/cm3 to 0.910 g/cm3, and an α-olefin having 4 to 8 carbons. However, this resin is not comprised of 3 components, as in the above example from the prior art.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an electro-beam cured sheet-type foam of improved tensile strength and dimensional stability.
It is another object of the present invention to provide an electron-beam cured sheet-type foam of improved tensile strength, dimensional stability and flexibility.
It is yet another object of the present invention to provide an electron-beam cured sheet-type foam of improved tensile strength at high temperatures and increased processability in molding wherein the foam is used in a composite material.
It is a further object of the present invention to provide an electron-beam cured sheet-type foam of improved dimensional stability whereby it may be more suitably used as a cushioning material in the automobile interiors.
It is yet another object of the present invention to provide an electron-beam cured sheet-type foam of improved tensile strength at high temperatures whereby it may be more suitably used as a heat-resisting and heat-insulating foamed material.
According to one aspect of the present invention, an electron-beam cured sheet-type foam comprises a polypropylene type resin (A) of 100 parts by weight of which main component is propylene; a copolymer resin (B) of 5 to 40 parts by weight, composed of ethylene and at least one selected from the group consisting of acrylic acid, ethylacrylate, maleic acid anhydride and vinylacetate; and a copolymer resin (C) of 10 to 80 parts by weight ethylene, of which melting point ranges from 117° C. to 123° C. and density ranges from 0.890 g/cm3 to 0.910 g/cm3, and an α-olefin having 4 to 8 carbons. This foam ranges from 20 to 60% in gel percent and from 5 to 40 in expansion ratio.
This foam may preferably be 50 kg/cm2.% or more in tensile strength at 150° C., and 5% or less in size-change ratio at 120° C., or size stability.
DETAILED DESCRIPTION OF THE INVENTION
The inventors have found that a foam of improved flexibility, tensile strength, dimensional stability, and processability in molding may be obtained by mixing the resins (A), (B) and (C) in a proper ratio, and by electron-beam curing prior to foaming.
COMPONENT
A polypropylene type resin (A) comprising propylene for use in a foam according to the present invention is, for example, a propylene homo-polymer; or a random copolymer, block copolymer or random/block copolymer of propylene, and at least one selected from the group consisting of ethylene and butane. The amount of ethylene and/or butene-1 in the copolymer may range from 2 to 35 weight percent, preferably from 3 to 30 weight percent. More preferably, the copolymer may be a random copolymer including ethylene of 4 to 15 weight percent.
The copolymer resin (B) may include ethylene and at least one compound of 5 to 30 weight percent (preferably, 8 to 25 weight percent) selected from the group consisting of acrylic acid, ethylacrylate, maleic acid anhydride and vinylacetate. More preferably, the copolymer (B) may be ethylene-ethylacrylate (EEA) comprising ethylacrylate of 8 to 18 percent, or a three-component copolymer of ethylene/ethylacrylate/maleic-acid-anhydride (EEA-MAH), including ethylacrylate and maleic acid anhydride of 8 to 18 weight percent in total.
The copolymer resin (C) of ethylene and α-olefin having 4 to 8 carbons ranges from 117° to 123° C. in melting point, and from 0.890 to 0.910 g/cm3 in density. Preferably, the copolymer (C) may include an α-olefin having 4 to 6 carbons, and may range from 117° to 123° C. in melting point and from 0.895 to 0.905 g/cm3 in density. The copolymer (C) of ethylene and α-olefin may be an ethylene/α-olefin copolymer as disclosed in Japanese Patent Laying-Open No. 157839/1983. There is a proportion between the density and the melting point of the copolymer, wherein the melting point increases as the density increases; but some physical characteristics of the resin, such as melting point, tensile strength, expansibility and flexibility, can be changed under a constant density, by using a different catalyst or a different mixing method. The copolymer (C) in the foam according to the present invention is different from the linear very-low-density polyethylene as described in Japanese Patent Laying-Open No. 265935/1988, viz., Ultzex (Mitsui Petrochemical Industries Ltd.) and Excelen (Sumitomo Chemical Co., Ltd.). For example, at density ranging from 0.890 to 0.910 g/cm3, the polyethylene used in Japanese Patent Laying-Open No. 265935/1988 has a melting point 4° to 7° C. lower than that used in the present invention. The lower melting point deteriorates the dimensional stability of the foam. At the same time the polyethylene used in the present invention has a higher melting point at low density, providing good flexibility and low size-change rate at 120° C.
According to the present invention, the mixing ratio of resin components (A), (B) and (C) is defined as follows: the component (A) is 100 parts by weight, the component (B) is 5 to 40 parts by weight (preferably, 5 to 25 parts by weight), and the component (C) is 10 to 80 parts by weight (preferably, 20 to 50 parts by weight). If the proportion of the component (B) is more than 40 parts by weight, the size stability (size-change rate at 120° C.) of the obtained foam becomes more than 5 percent. If the proportion of component (B) is lower than 5 parts by weight, the obtained foam cannot satisfy the required levels of flexibility, heat resistance, tensile strength and molding processability. Particularly, the obtained foam lacks sufficient tensile strength at high temperatures. Moreover, if the proportion of the component (B) is lower than 5 parts by weight, the obtained foam has the same characteristics as those of a foam made from a mixture of the components (A) and (C). If a foam contains an excess of the component (A), the obtained foam lacks sufficiently high flexibility, although it has high shock resistance and dimensional stability. If a foam contains an excess of the component (C), the obtained foam has inferior heat resistance, although it has high flexibility. If the proportion of the component (C) is less than 10 parts by weight, the flexibility of the obtained foam deteriorates. Moreover, if the proportion of the component (C) is more than 80 parts by weight, the size stability deteriorates, although good flexibility may be obtained.
GEL PERCENT AND EXPANSION RATE
According to the present invention, the foam ranges from 20 to 60 percent in gel percent and from 5 to 40 in expansion rate.
If the gel percent is lower than 20 percent, the dimensional stability of the obtained foam deteriorates due to gel shortage. Furthermore, the predetermined density cannot be obtained and the formed surfaces of the foam are rough, due to the fact that a gas is generated inside the foam during production which disrupts the surfaces. Moreover, sufficient tensile strength at high temperatures cannot be obtained. If the gel percent is more than 60 percent, the obtained foam tends too strongly to retain its shape resulting in greater than 5 percent of dimensional stability (size-change rate at 120° C.). The flexibility also deteriorates.
The expansion ratio must range from 5 to 40. If the expansion ratio is lower than 5, the flexibility deteriorates inasmuch as the foam becomes too hard, although the tensile strength and the molding processability remain sufficient. If the expansion rate is more than 40, the shock-absorbing ability deteriorates inasmuch as the obtained foam becomes too soft, although the flexibility remains sufficient.
TENSILE STRENGTH
According to the present invention, the foam may be 50 kg/cm2.% or more in tensile strength at 150° C. If the tensile strength is lower than 50 kg/cm2.%, the obtained foam becomes ruptured, because the tensile strength of the foam is not sufficient at high temperatures to correspond with the expansion and the expansion stress of the facing material (such as a sheet of vinylchloride), when the foam is heat-processed after being laminated with the facing material.
Cured foams made of conventional resin proportions have a problem in that only a few kinds of facing material may be used in a heat molding process due to the low expansion stress of the foams. However, foam according to the present invention has 50 kg/cm2.% or more in tensile strength, so that it is superior to conventional foams. Foam according to the present invention is of improved tensile strength at high temperatures, whereby less disuniformity in thickness of product occurs, and heat-molding processability is improved. The molding processability (L/D) can be expanded to 1.2.
DIMENSIONAL STABILITY
The dimensional stability (size-change rate at 120° C.) of a foam according to the present invention is preferably 5 percent or less. If the dimensional stability is more than 5 percent, foam shrinkage is so great that products in which the inclusion of a heat-process method is essential cannot be obtained.
COMPRESSIVE HARDNESS AND STRESS
The 25%-compressive hardness of the foam according to the present invention preferably ranges from 0.1 to 1.0 kg/cm2 at ordinary temperatures. If the compressive hardness is more than 1.0 kg/cm2, the tensile strength of foam becomes so great that its tactility deteriorates. If the compressive hardness is lower than 0.1 kg/cm2, the foam becomes so soft that a "reaching-bottom feeling" results (i.e., a feeling of reaching the opposite surface when the foam is pressed by a finger). Furthermore, foam of weak tensile strength deteriorates handling characteristics in manufacturing and transforming processes.
The 5%-tensile stress of the foam according to the present invention may range from 10 to 100 kg/cm2 at ordinary temperature. If the stress is more than 100 kg/cm2, the shock absorbing ability deteriorates and the tensile strength becomes too great. If the stress is lower than 10 kg/cm2, the tensile strength becomes too weak, although the flexibility is adequate.
The 25%-compressive hardness and the 5%-tensile stress at ordinary temperature may be used as a measure of suppleness flexibility. Foams of which characteristics are within the above ranges will have suppleness noticeably different from those of conventional foams, when such foams are evaluated after they are laminated with various kinds of facing material and processed to form products.
SHEET
The foam according to the present invention is a sheet. The foam may be more than 10 m long, and may be rolled in forming a material product. The long sheet may be processed in several continuous manufacturing steps in order to decrease losses during the steps.
MANUFACTURING STEPS
A method for manufacturing a foam according to the present invention will henceforth be described.
The resin components (A), (B) and (C), powdered into 32-mesh-passing size, are provided, of which proportions are within the ranges of the present invention. The components are fed into a high-speed mixing apparatus (such as a Henschel mixer or a super mixer). Furthermore, an ordinary chemical foaming agent of the decomposable type (for example, azodicarbonamide, dinitrosopentamethylene-tetramine, etc.) of 2 to 20 parts by weight is added to the resin components of 100 parts by weight. At the same time, other additives may also be included. Thereby, initial mixing is carried out. The obtained material is fed into an extruder heated at 130° to 190° C., and melt-diffusion mixing is effected, producing a long sheet which is 0.5 to 6 mm in thickness. In the mixing steps, it is important that the forming agent be decomposed as little as possible.
The obtained sheet must be cured in order not to allow interior gas generated by the decomposition of the foaming agent to escape during the foaming process. In order to cure the sheet, a conventional ionizing radiation method may be used. A conventional peroxide compound can be added prior to irradiation; furthermore, if desired, a multi-functional monomer of divinylbenzene, trimethylolpropane triacrylate, pentaerythritol triacrylate, etc.; a multi functional dimer of those; or a multi functional trimer of those may be added as a crosslinking promoting agent. Added within the scope of the present invention may be an inorganic filler such as calcium carbonate, talc, glass balloon, glass fiber, etc.; an antistatic agent; a flame retarder; and a colorant.
The obtained cured sheet is introduced into a heated-air atmosphere or onto a chemical liquid such as silicon oil, of which temperature is 10° to 100° C. higher than the decomposing temperature of the foaming agent, whereby the foaming agent is rapidly decomposed to make the sheet-type cured foam.
If a corona discharging process is applied to at least one surface of the obtained foam, whereby the surface-wetting tension is more than 37 dyne/cm, the foam will be sufficiently adhesive to coating materials. A foam having an adhesive layer, or a cohesive layer formed of a coating material, can be laminated with a sheet of facing material, a film, another kind of foam, a metallic foil, a sheet of paper, a piece of nonwoven fabric made of natural fiber or synthetic fiber, or a piece of synthetic leather. The obtained laminated product can be molded by various methods.
PARAMETERS
The parameters will be explained in the following:
(a) Melting Point (°C.)
The melting point is a temperature at the highest peak of endothermic peaks in measurement with a differential spectrum calorimeter (DSC).
(b) Density (g/cm3)
The density is measured in accordance with JISK6767.
(c) Gel Percent (%)
The foam to be measured is broken into small pieces, and 0.2 g pieces of the foam are selected by accurate weighing. The weighed pieces are soaked in tetralin at 135° C. for 2 hours, to elute soluble substances. Then, the insoluble part is taken out from the tetralin, and the tetralin remaining in the insoluble part is removed by acetone. The acetone is removed by hot water at 40° C. The insoluble part is then dried in a vacuum drier at 100° C. for 1 hour, and the weight w1(g) of the insoluble part is measured. The gel percent (%) is calculated by the following formula, wherein 10 pieces of the foam should be used.
Gel Percent (%)=(w1/0.2)×100
(d) Expansion Rate
A 10×10-cm piece is taken from a sheet-type foam. The piece is measured with respect to its thickness t (cm) and its weight w2 (g). The expansion rate is calculated by the following formula, wherein 10 sample pieces are used.
Expansion Rate=1/(w2/[10×10×t])
(e) Tensile Strength at 150° C. (kg/cm2.%)
A 1×10-cm piece is taken from a sheet-type foam, and measured with respect to its thickness t(cm). The piece of foam is set between chucks in a tensilon-type tensile tester within a heat box at 150° C. The distance between the chucks is 5 cm. The piece of foam is protected by paper or the like at the chucked portions, so that it will not be fractured at those portions. 5 minutes after the piece is set in the heat box, the piece is stretched at a tensile speed of 200 mm/min. The rupture stress s1(kg) and the rupture extension s2(cm) are recorded on a sheet of record paper.
The tensile strength at 150° C. (kg/cm2.%) can be calculated by the following formula, wherein 5 pieces of foam are used. ##EQU1## where s1 is 0.3 kg/cm2 or more, s2 is 100% or more.
(f) Size-Change Rate at 120° C. (Dimensional Stability) (%)
A 10×10-cm piece is taken from a sheet-type foam, and measured in thickness t(mm) at the center. The piece is heated for 1 hour in a hot air drier at 120° C. Subsequently, the piece is left for 2 hours at room temperature, and then its size is measured. The 120° C.-Size-Change rate (%) can be calculated by the following formula. ##EQU2## where TD signifies the lengthwise direction, MD signifies the widthwise direction.
(g) 25% Compressive Hardness at Ordinary Temperature (kg/cm2)
The Compressive Hardness is measured in accordance with JIS K-6767.
(h) 5% Expansion Stress at Ordinary Temperature (kg/cm2)
A 1×10-cm piece is taken from a sheet-type foam, and its thickness t(cm) is measured. The piece is set between chucks separated by a distance of 5 cm in a tensilon-type tensile tester, and stretched at 20 mm/min. The changes of stress and elongation are recorded on a sheet of paper, and then the stress s1 (kg) of the piece is measured when it has been stretched five percent. The 5%-expansion stress at ordinary temperature is calculated by the following formula.
5%-expansion Stress (kg/cm.sup.2) at ordinary temperature=s1/(1×t)
(i) Molding Processability (L/D)
Cylindrical metal molds of which the depth (L)/diameter(D) ratio varies at intervals of 0.05 are used. A foam or laminated sheet is vacuum-molded at 160° to 180° C. by a vacuum molding machine. The maximum ratio at which the foam forms a molding without any breaks is determined as the value of molding processability.
Molding Processability (L/D)=L/D
EXAMPLES
Tables 1A and 1B show the resin composition, the mixing ratio, the curing methods and the characteristics of the foams according to the present invention. In the tables, "random" means random copolymer, "block" means block copolymer, and "homo" means homo polymer. "EPC" means propylene/ethylene copolymer, "BPC" means propylene/butane copolymer, "EEA" means ethylene/ethylacrylate, "EVA" means ethylene/vinylacetate copolymer, and "EEA.MAH" means (ethylene/ethylacrylate/maleicacid-anhydride) terpolymer. "Et-Bt" of ethylene/α-olefin copolymer means a copolymer formed by the polymerization of ethylene with butane as an α-olefin. The low-density polyethylene is made by the high pressure method, and the high-density polyethylene is made by the low pressure method. The linear very-low-density polyethylene is a polyethylene of which density is 0.910 g/cm3 or lower, and which is made by the high-pressure ion polymerization method and the intermediate-low-pressure solution polymerization method.
Examples according to the present invention and comparative examples will henceforth be described.
One-hundred-fifty-kg mixtures of the resin components, a foaming agent, and other additives were each fed into a 500-litter Henschel mill. Each portion of the obtained mixed material was fed into an extruder of which cylinder temperature was 170° to 180° C. to carry out melt-mixing, whereby a long sheet of 1.5 mm thickness and 500 mm width was formed. The long sheet was set in an electron-beam irradiating device, and then it was cured with 2 to 10 Mrad electron-beam radiation. The obtained foamable cured sheet was introduced uniformly onto silicon oil of which temperature ranges from 210° to 240° C., thereby foaming the sheet. The foamed sheet was dried by hot air, whereby a sheet-type cured foam was obtained. The obtained foams ranged from 2.5 to 3.5 mm in thickness and from 950 to 1100 mm in width. The foams according to the present invention, as shown in Table 1B, had high degrees of flexibility, tensile strength, dimensional stability and molding processability, since the resin components, the mixing ratio, the curing method and the cross-linking density were chosen appropriately. Particularly, 25%-compressive hardness and 5%-expansion stress as parameters of flexibility were superior, so that the obtained flexible foams had a good tactility. Furthermore, the obtained foams had a tensile strength at high temperature which had not been achieved by conventional foams.
Tables 2A and 2B show the resin component, the mixing ratio, the curing method and the characteristics of the obtained foams with regard to comparative examples. The comparative examples were cured by the electron-beam curing method in the same manner as in the examples according to the present invention, or in the curing method with peroxide compounds, and foamed in the same way as in the examples according to the present invention.
Comparative examples 1 to 3 were made of ethylene/α-olefin copolymer. As shown in Table 2B, the comparative examples were inferior, at least in terms of flexibility, tensile strength and dimensional stability, since the resin components, the mixing ratio and the curing method were apart from the scope of the present invention. In particular, the comparative examples were much inferior in terms of tensile strength at high temperature and 120° C. size-change rate. Comparative examples 4 to 7 were made of linear very-low-density polyethylene (EXCELEN). As shown in Table 2B, the comparative examples were inferior, at least in terms of flexibility, tensile strength and dimensional stability, since the resin components, the mixing ratio and the curing method were apart from the scope of the present invention. Comparative examples 4 to 7, as well as Comparative examples 1 to 3, were noticeably inferior to the examples according to the present invention in terms of tensile strength at high temperature and 120° C. size-change rate. In the tables, the parts marked by an asterisk are apart from the scope of the present invention.
As which have been described above, the foams according to the present invention are superior in terms of flexibility, or tactility in particular. A high degree of molding processability can be obtained in accordance with the present invention, because the foams have a high degree of tensile strength, particularly at high temperatures. Furthermore, the foams according to the present invention also have sufficient dimensional stability, whereby they may be suitable as a damping material, for application to the doors, the ceiling, the instrument panel, etc. of automobiles interiors. The foams according to the present invention can be also applied to the base material of heat-resist adhesive tape, the base material of packagings, and heat-resisting and heat-insulate molding products, including various kinds of valves and pipes, etc., by virtue of the above characteristics.
                                  TABLE 1A                                
__________________________________________________________________________
       RESIN COMPONENT        CROSS                                       
                      (C)     LINKING       MIXING                        
              (B)     ETHYLENE/                                           
                              AGENT/        RATIO       GEL               
       (A)    ETHYLENE                                                    
                      α-OLEFIN                                      
                              FOAMING       A   B   C   PERCENT           
EXAMPLE                                                                   
       PP     COPOLYMER                                                   
                      COPOLYMER                                           
                              AGENT  CURING wt %                          
                                                wt %                      
                                                    wt %                  
                                                        (%)               
__________________________________________________________________________
1      RANDOM EEA     Et-Bt   --/    ELECTRON                             
                                            100 17  50  38                
       EPC    EA 18%  MI 5    AC 10% BEAM                                 
       Et 5%  MI 7    DENSITY                                             
       MI 2           0.907                                               
                      MELTING                                             
                      POINT                                               
                      120° C.                                      
2      RANDOM EEA     Et-Bt   --/    ELECTRON                             
                                            100 6.5 19  40                
       EPC    EA 8%   MI 5    AC 12% BEAM                                 
       Et 13% MI 7    DENSITY                                             
       MI 2           0.919                                               
                      MELTING                                             
                      POINT                                               
                      123° C.                                      
3      RANDOM EEA.MAH Et-Bt   --/    ELECTRON                             
                                            100 15  20  30                
       EPC    EA.MAH 18%                                                  
                      MI 5    AC 8%  BEAM                                 
       Et 13% MI 7    DENSITY                                             
       MI 2           0.905                                               
                      MELTING                                             
                      POINT                                               
                      119° C.                                      
4      RANDOM EVA     Et-Bt   --/    ELECTRON                             
                                            100 40  40  35                
       EPC    VA 14%  MI 5    AC 13% BEAM                                 
       Et 15%         DENSITY                                             
       MI 4           0.897                                               
                      MELTING                                             
                      POINT                                               
                      119° C.                                      
5      HOMO PP                                                            
              EEA     Et-Bt   --/    ELECTRON                             
                                            100 20  80  35                
       --     EA 8%   MI 5    AC 13% BEAM                                 
              MI 7    DENSITY                                             
                      0.890                                               
                      MELTING                                             
                      POINT                                               
                      117° C.                                      
__________________________________________________________________________

                                  TABLE 1B                                
__________________________________________________________________________
                                                    DIMENSIONAL           
              FLEXIBILITY                           STABILITY             
              COMPRES-                                                    
                     5%      TENSILE STRENGTH                             
                                             MOLDING                      
                                                    120° C.        
       FOAMING                                                            
              SIVE   EXPANSION                                            
                             ORDINARY        PROCES-                      
                                                    SIZE-CHANGE           
       RATE   HARDNESS                                                    
                     STRESS  TEMP.  150° C.                        
                                             SABILITY                     
                                                    RATE (%)              
EXAMPLE                                                                   
       (%)    kg/cm.sup.2                                                 
                     kg/cm.sup.2                                          
                             kg/cm.sup.2 · %                     
                                    kg/cm.sup.2 · %              
                                             (L/D)  MD  TD  ZD            
__________________________________________________________________________
1      20     0.48   60      4200   55       0.76   -3.2                  
                                                        -2.1              
                                                            4.0           
                                    (STRENGTH                             
                                    0.3 kg/cm.sup.2                       
                                    ELONGATION                            
                                    180%)                                 
2      25     0.40   50      3800   60       0.85   -2.8                  
                                                        -1.9              
                                                            3.1           
                                    (STRENGTH                             
                                    0.3 kg/cm.sup.2                       
                                    ELONGATION                            
                                    200%)                                 
3      15     0.96   95      1400   147      0.95   -2.1                  
                                                        -1.1              
                                                            2.8           
                                    (STRENGTH                             
                                    0.6 kg/cm.sup.2                       
                                    ELONGATION                            
                                    245%)                                 
4      25     0.57   25      2500   90       0.62   -3.5                  
                                                        -2.7              
                                                            4.6           
                                    (STRENGTH                             
                                    0.45 kg/cm.sup.2                      
                                    ELONGATION                            
                                    200%)                                 
5      25     0.68   75      9600   70       0.88   -0  -0  0             
                                    (STRENGTH                             
                                    0.35 kg/cm.sup.2                      
                                    ELONGATION                            
                                    200%)                                 
__________________________________________________________________________

                                  TABLE 2A                                
__________________________________________________________________________
                              CROSS                                       
       RESIN COMPONENT        LINKING     MIXING      GEL FOAM-           
COMPAR-       ETHYLENE                                                    
                     ETHYLENE/                                            
                              AGENT/      RATIO       PER-                
                                                          ING             
ATIVE         CO-    α-OLEFIN                                       
                              FOAMING                                     
                                     CUR- A   B   C   CENT                
                                                          RATE            
EXAMPLE                                                                   
       PP     POLYMER                                                     
                     COPOLYMER                                            
                              AGENT  ING  wt %                            
                                              wt %                        
                                                  wt %                    
                                                      (%) (%)             
__________________________________________________________________________
1      --     --     Et-Bt    DCP 0.8%/                                   
                                     --   --  --  100 60  25              
       *      *      MI 2     AC 13% HEAT-                                
                                          *   *   *                       
                     DENSITY 0.907                                        
                              *      ING                                  
                     MELTING                                              
                     POINT                                                
                     121° C.                                       
2      RANDOM --     Et-Bt    DCP 0.8%/                                   
                                     --   100 --  230 50   8              
       EPC    *      MI 2     AC 7%  HEAT-    *   *                       
       Et 5%         DENSITY 0.905                                        
                              *      ING                                  
       MI 2          MELTING         *                                    
                     POINT                                                
                     120° C.                                       
3      RANDOM EEA    Et-Bt    DCP 0.8%/                                   
                                     --   100 30  100 55  20              
       EPC    EA 18% MI 5     AC 10% HEAT-        *                       
       Et 5%  MI 7   DENSITY 0.900                                        
                              *      ING                                  
       MI 2          MELTING         *                                    
                     POINT                                                
                     119° C.                                       
4      LOW-   --     EXCELEN  --/    ELEC-                                
                                          100 --  100 28  15              
       DENSITY                                                            
              *      MI 10    AC 6%  TRON     *   *                       
       POLY-         DENSITY 0.900   BEAM                                 
       ETHYLENE      MELTING                                              
       MI 14         POINT                                                
       DENSITY       115° C.                                       
       0.921                                                              
       *                                                                  
5      RANDOM HIGH-  EXCELEN  --/    ELEC-                                
                                          100 85  100 50  30              
       EPC    DENSITY                                                     
                     MI 10    AC 13% TRON     *   *                       
       Et 5%  POLY-  DENSITY 0.890   BEAM                                 
       MI 2   ETHYLENE                                                    
                     MELTING                                              
              MI 6.5 POINT                                                
              DENSITY                                                     
                     114° C.                                       
              0.957                                                       
              *                                                           
6      RANDOM EEA    EXCELEN  --/    ELEC-                                
                                          100 30  200 35  20              
       EPC    EA 18% MI 10    AC 10% TRON         *                       
       Et 5%  MI 7   DENSITY 0.900   BEAM                                 
       MI 2          MELTING                                              
                     POINT                                                
                     115° C.                                       
7      RANDOM EVA    EXCELEN  DCP 1.5%/                                   
                                     --   100 50  40  65  45              
       EPC    VA 15% MI 10    AC 18% HEAT-    *       *                   
       Et 5%  MI 7   DENSITY 0.895                                        
                              *      ING                                  
       MI 2          MELTING         *                                    
                     POINT                                                
                     113° C.                                       
__________________________________________________________________________

                                  TABLE 2B                                
__________________________________________________________________________
                                               DIMENSIONAL                
       FLEXIBILITY      TENSILE                STABILITY                  
                5%      STRENGTH        MOLDING                           
                                               120° C.             
COMPAR-                                                                   
       COMPRESSIVE                                                        
                EXPANSION                                                 
                        ORDINARY        PROCES-                           
                                               SIZE-CHANGE                
ATIVE  HARDNESS STRESS  TEMP.  150° C.                             
                                        SABILITY                          
                                               RATE (%)                   
EXAMPLE                                                                   
       kg/cm.sup.2                                                        
                kg/cm.sup.2                                               
                        kg/cm.sup.2                                       
                               kg/cm.sup.2 · %                   
                                        (L/D)  MD   TD    ZD              
__________________________________________________________________________
1      0.40     4        600   13       0.55   -25.0                      
                                                    -22.9 35.8            
                *              (STRENGTH       *    *     *               
                               0.1 kg/cm.sup.2                            
                               ELONGATION                                 
                               130%)                                      
                               *                                          
2      1.55     25      4000   28       0.64   -13.0                      
                                                    -10.5 17.5            
       *                       (STRENGTH       *    *     *               
                               0.14 kg/cm.sup.2                           
                               ELONGATION                                 
                               200%)                                      
                               *                                          
3      0.50     9       2800   42       0.60   -15.0                      
                                                    -14.3 16.8            
                *              (STRENGTH       *    *     *               
                               0.21 kg/cm.sup.2                           
                               ELONGATION                                 
                               200%)                                      
                               *                                          
4      0.48     13      2900   25       0.60   -35.0                      
                                                    -32.9 -42.1           
                               (STRENGTH       *    *     *               
                               0.2 kg/cm.sup.2                            
                               ELONGATION                                 
                               125%)                                      
                               *                                          
5      0.65     105     5800   45       0.55    -3.1                      
                                                     -2.4  4.0            
                *              (STRENGTH                                  
                               0.25 kg/cm.sup.2                           
                               ELONGATION                                 
                               180%)                                      
                               *                                          
6      0.48     20      3100   32       0.60   -13.0                      
                                                    -10.3 19.8            
                               (STRENGTH       *    *     *               
                               0.16 kg/cm.sup.2                           
                               ELONGATION                                 
                               200%)                                      
                               *                                          
7      0.08     30.5    2500   45       0.35    -8.5                      
                                                     -6.8  9.9            
       *                       (STRENGTH       *    *     *               
                               0.30 kg/cm.sup.2                           
                               ELONGATION                                 
                               150%)                                      
                               *                                          
__________________________________________________________________________

Claims (10)

We claim:
1. An electron-beam cured sheet-type foam comprising 100 parts by weight of a polypropylene type resin (A) the main component of which is propylene; 5 to 40 parts by weight of a copolymer resin (B) which is made up of ethylene and at least one comonomer selected from the group consisting of acrylic acid, ethylacrylate, maleic acid anhydride and vinylacetate; and a copolymer resin (C) made up of ethylene and an alpha olefin containing 4 to 8 carbon atoms, having a melting point of 117° C. to 123° C. and a density of 0.890 g/cmg/cm3 to 0.910 g/cm3 ; which foam sheet has a gel content of 20 to 60 percent, an expansion ratio of 5 to 40 a toughness at 150° C. of 50 kg/cm2 % or more, a size-change ratio at 120° C. of 5 percent or less, a 25%-compressive hardness at ordinary temperature of 0.1 to 1.0 kg/cm2 and a 5%-expansion stress at ordinary temperature of 10 to 100 kg/cm2.
2. A foam according to claim 1, wherein the parts by weight of said polypropylene type resin (A) is 100, the parts by weight of said copolymer (B) ranges from 5 to 25, and the parts by weight of said copolymer (C) ranges from 20 to 50.
3. A foam according to claim 2, wherein said copolymer (C) is a copolymer including an α-olefin of 4 to 6 carbons having a melting point of 117° to 123° C., and a density of 0.895 to 0.905 g/cm3.
4. A foam according to claim 3, wherein said copolymer (B) includes 5 to 30 weight percent of said comonomer.
5. A foam according to claim 4, wherein said copolymer (B) includes 8 to 25 weight percent of said comonomer.
6. A foam according to claim 5, wherein said copolymer (B) is one selected from the group consisting of a two component copolymer of ethylene/ethyl-acrylate copolymer, which contains 8 to 18 weight percent ethyl acrylate; and a three-component copolymer of ethylene/ethylacrylate/maleic-acid-anhydride, which contains 8 to 18 weight percent of ethyl acrylate and maleic acid anhydride in total.
7. A foam according to claim 6, wherein said polypropylene type resin (A) is a polymer selected from the group consisting of a propylene homo-polymer; and a random copolymer, block copolymer and random/block copolymer, including propylene and at least one comonomer selected from the group consisting of ethylene and butene.
8. A foam according to claim 7, wherein said polypropylene type resin (A) is a copolymer containing propylene and 2 to 35 weight percent of a comonomer.
9. A foam according to claim 8, wherein said polypropylene type resin (A) is a copolymer containing 3 to 30 weight percent of said comonomer.
10. A foam according to claim 9, wherein said polypropylene type resin (A) is a random copolymer including 4 to 15 weight percent ethylene.
US07/598,646 1989-05-16 1990-05-14 Electron-beam cured sheet-type foam Expired - Lifetime US5110842A (en)

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WO (1) WO1990014385A1 (en)

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US5786406A (en) * 1995-02-08 1998-07-28 Toray Industries, Inc. Polyolefin based crosslinked foam
US6258862B1 (en) * 1996-07-02 2001-07-10 Solvay (Société Anonyme) Composition based on polyolefins and on ethylene-vinyl acetate copolymer
WO2002018482A2 (en) * 2000-08-29 2002-03-07 Jsp Corporation Extruded polyolefin resin foam
US6541533B2 (en) 2001-01-10 2003-04-01 Jsp Corporation Extruded polyolefin resin foam
US20060154998A1 (en) * 2003-06-27 2006-07-13 Mitsui Chemicals, Inc. Resin composition for foam and use thereof
WO2013043944A1 (en) 2011-09-23 2013-03-28 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
EP3604412A4 (en) * 2017-03-31 2021-05-19 Sekisui Chemical Co., Ltd. Foam and molded article

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JP2918412B2 (en) * 1993-04-01 1999-07-12 積水化学工業株式会社 Polyolefin resin foam
US7173070B2 (en) 2001-02-23 2007-02-06 Phat Cushion Llc Foam cushion and method of making and using the same
WO2002068515A1 (en) * 2001-02-23 2002-09-06 Phat Cushion Llc Foam cushion and method of making and using the same
US7040706B2 (en) 2002-12-09 2006-05-09 Phat Cushion Llc Seat and method of making same
JP4563109B2 (en) * 2003-08-22 2010-10-13 日東電工株式会社 Method for producing foam dustproof material, and method for producing dustproof structure using foam dustproof material
DE10356665A1 (en) * 2003-12-04 2005-07-07 Benecke-Kaliko Ag Process for the production of grained shaped articles and the molded articles produced therefrom
ATE410468T1 (en) * 2005-08-08 2008-10-15 Alveo Ag SOFT POLYOLEFINE FOAM WITH HIGH HEAT RESISTANCE
JP2008255287A (en) * 2007-04-09 2008-10-23 Toray Ind Inc Polyolefin crosslinked resin foam capable of easy adhesion
JP5417890B2 (en) * 2009-02-25 2014-02-19 東レ株式会社 Crosslinked resin foam for plating
US9260577B2 (en) 2009-07-14 2016-02-16 Toray Plastics (America), Inc. Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength
CN103467842B (en) * 2013-08-22 2015-11-25 湖北祥源新材科技有限公司 A kind of electron accelerator irradiation is cross-linked virgin pp foam sheet and preparation method

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JPS6234930A (en) * 1985-08-06 1987-02-14 Toray Ind Inc Crosslinked polypropylene resin foam having excellent heat-resistance and formability
JPS63159447A (en) * 1986-12-22 1988-07-02 Japan Styrene Paper Co Ltd Crosslinked polyolefin resin foam and its production

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JPS63159447A (en) * 1986-12-22 1988-07-02 Japan Styrene Paper Co Ltd Crosslinked polyolefin resin foam and its production

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5786406A (en) * 1995-02-08 1998-07-28 Toray Industries, Inc. Polyolefin based crosslinked foam
US6258862B1 (en) * 1996-07-02 2001-07-10 Solvay (Société Anonyme) Composition based on polyolefins and on ethylene-vinyl acetate copolymer
WO2002018482A2 (en) * 2000-08-29 2002-03-07 Jsp Corporation Extruded polyolefin resin foam
WO2002018482A3 (en) * 2000-08-29 2002-09-26 Jsp Corp Extruded polyolefin resin foam
US6541533B2 (en) 2001-01-10 2003-04-01 Jsp Corporation Extruded polyolefin resin foam
US20060154998A1 (en) * 2003-06-27 2006-07-13 Mitsui Chemicals, Inc. Resin composition for foam and use thereof
WO2013043944A1 (en) 2011-09-23 2013-03-28 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
US9365711B2 (en) 2011-09-23 2016-06-14 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
EP3604412A4 (en) * 2017-03-31 2021-05-19 Sekisui Chemical Co., Ltd. Foam and molded article

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KR0157309B1 (en) 1998-12-01
WO1990014385A1 (en) 1990-11-29
JPH0645717B1 (en) 1994-06-15
EP0425695B1 (en) 1996-12-18
DE69029458T2 (en) 1997-05-28
EP0425695A4 (en) 1992-07-08
EP0425695A1 (en) 1991-05-08
DE69029458D1 (en) 1997-01-30
KR920700253A (en) 1992-02-19

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